KR19990007217A - Cleaning method of liquid raw material evaporator and CVD system - Google Patents

Abstract

The present invention provides an evaporation vessel of a metal into which a liquid raw material is injected, a heater for heating the evaporation vessel to evaporate the liquid injected into the evaporation vessel, and a metal nozzle positioned in the evaporation vessel in such a manner as to be electrically insulated from the evaporation vessel. It relates to an evaporation apparatus provided with (electrode means). The evaporation apparatus of the present invention also provides a cleaning solution supply device for supplying a cleaning solution for dissolving residues generated in the evaporation vessel to the inside of the evaporation vessel, and the nozzle for generating a plasma in the evaporation vessel using the evaporated cleaning solution. And a plasma generating power supply for supplying high frequency power to a position between the evaporation vessel and the evaporation vessel.

Description

Cleaning method of liquid raw material evaporator and CD unit

The present invention provides a substrate by a CVD method using a metal organic chemical vapor deposition apparatus (hereinafter referred to as MOCVD apparatus) or an evaporator for evaporating a liquid raw material by applying heat and a raw material evaporated in the evaporator. Another method of cleaning a CVD apparatus having a process chamber for forming a thin film on the substrate is provided. In particular, the present invention relates to a method for removing residues in an evaporator and a process chamber.

Liquid raw materials, which are generally liquid at room temperature, are supplied in the evaporated state by the method disclosed in Japanese Patent Laid-Open No. 50-211072 and using a so-called bubbler or bubbling device. Further, in the semiconductor manufacturing process, the method is used in many film forming apparatuses including an apparatus for forming a tetraethoxy orthosilane (hereinafter referred to as TEOS) film or an apparatus for forming a superconducting thin film.

Recently, a dielectric thin film has attracted attention as an important technology for manufacturing next generation dynamic random access memory (DRAM) and ferroelectric random access memory (FRAM) devices. The dielectric and ferroelectric thin films include, for example, a BST (BaSrTiO ₃ , ie, barium strontium titanate) film and an SrTiO ₃ (strontium titanate) film.

In the case where the dielectric thin film is formed by a CVD apparatus, a metal organic material such as Ba (DPM) ₂ , Sr (DPM) ₂ , or Pb (DPM) ₂ is used (where DPM is dipivaloyl methane). being). Each of the aforementioned materials must be maintained at a high temperature not lower than about 200 ° C. because they are high temperature at room temperature, and thus remain liquid when the material is supplied in a gaseous state by the bubbling device. However, it is known that such a raw material decomposes rapidly and deteriorates in the high temperature state mentioned above.

In order to realize a liquid state at a relatively low temperature, a method of dissolving a metal organic material (solid material) in an additive (solvent type) such as THF (tetrahydrofuran) has been developed. When vaporized material is supplied by a bubbling device, a pipe disposed from the bubbling device to the processing chamber should be maintained at a temperature of 200 ° C. or higher to prevent condensation or liquefaction of the material. Therefore, the hot pipe state must be maintained. In this case, only an additive such as THF decomposes and evaporates, and thus, a necessary material, for example, Sr (DPM) ₂ , condenses and becomes fixed inside the pipe.

In order to solve the above-mentioned problems, recently, the liquid raw material obtained by dissolving the required solid raw material in a solvent is supplied in a liquid state, and then the raw material is evaporated by heating in an evaporator provided in front of the processing chamber, and then immediately in the processing chamber. Research into the method of supplying the inside of the car is beginning.

A CVD apparatus equipped with the evaporator described above is disclosed in Japanese Patent Laid-Open No. 7-268634. An example of a CVD apparatus is shown in FIG. 4.

A predetermined amount of the liquid raw material 4 obtained by dissolving the required solid raw material such as Sr (DPM) ₂ in a solvent such as THF from the liquid raw material supply device 2 to the evaporator 8 through the liquid raw material pipe 6. Supply.

According to this example, the liquid raw material supply device 2 comprises a liquid raw material container 42 for receiving the liquid raw material 4, valves 44 to 47, a flow control means 48 and a pipe connecting these components. Equipped. The liquid raw material container 42 is supplied with an inert gas 50 to send the liquid raw material 4 using the pressure through the valve 44. The inert gas 50 is composed of at least nitrogen gas or rare gas (ie, He, Ne, Ar, Kr, Xe or Rn, etc.). When the liquid raw material is supplied using pressure, the valves 44, 45 and 47 are opened and the valve 46 is closed.

The evaporator 8 has a structure in which the gas injection pipe 16 is connected to the evaporation vessel 10. In particular, the nozzle 14 is inserted into the evaporation vessel 10 coaxially with the gas injection pipe 16. The heater 12 is arranged around the evaporation vessel 10. The nozzle 14 is connected to the liquid raw material pipe 6. The inert gas 18 is supplied to the gas injection pipe 16 through the flow rate adjusting means 17. This inert gas 18 is composed of at least one of nitrogen gas and rare gas.

The liquid raw material 4 supplied to the evaporator 8 is roughly granulated by the high speed inert gas 18 flowing around the tip at the tip of the nozzle 14. The liquid raw material 4 is then dispersed and collides with the extensive inner wall of the evaporation vessel 10 heated to a temperature not lower than 250 ° C., so that the liquid raw material 4 is immediately evaporated. The evaporated raw material 20 passes through the evaporated raw material pipe 22 and the valve 24 and is then supplied into the process chamber 26.

The process chamber 26 is provided with a holder (also known as a susceptor) 36 for supporting the substrate 34 (here, a film is formed) and has a number of small openings and diffuses gas injected into the process chamber 26. It is provided with a gas diffusion plate 32 arranged to make. The holder 36 and the substrate 34 disposed on the holder 36 are heated by heating means (not shown). Vacuum exhaust treatment means 40 for evacuating the interior of the treatment chamber 26 is connected to the treatment chamber 26 via a valve 38. In addition to the evaporated raw material 20, a gas 30 arranged to react with the evaporated raw material 20 is injected into the process chamber 26. When a thin film made of SrTiO ₃ is formed, the gas 30 is a mixed gas of TTIP (Ti (0-iC ₃ H ₇ )) and an oxide gas (O _2, etc.). The vaporized raw material 20 and the gas 30 are mixed in the processing chamber 26. The mixed gas is dispersed to have a constant flow rate by the gas diffusion plate 32 and then diffused into the vacuum evacuation process chamber 26 by the vacuum exhaust treatment means 40. The mixed gas then comes into contact with the heating surface of the substrate 34. As a result of the CVD reaction, a thin film made of SrTiO ₃ or the like is formed. The mixed gas which is not used to form the thin film is discharged to the outside through the vacuum exhaust treatment means 40.

Raw materials such as Sr (DPM) ₂ or Ba (DPM) ₂ described above are easily combined with trace impurities such as H ₂ O, CO, CO ₂ , and precipitate. If the ambient temperature is high, the raw material gradually degrades and precipitates due to the change of time. Residues of the raw material accumulate in the evaporator 8 (especially the evaporation vessel 10 of the evaporator 8), causing a number of problems. For example, the residue is fixed to the inner wall of the evaporation vessel 10, thereby lowering the evaporation efficiency of the liquid raw material 4 or the fixed state is not uniform. As a result, evaporation becomes unstable. Moreover, residue sometimes clogs the nozzles 14. Also, if a fixed residue is released, this means that the downstream valve or pipe is blocked.

In order to prevent this, a washing solution (eg, nitric acid) capable of dissolving the residue is periodically used for internal cleaning of the evaporation vessel 10. The exhaust gas 21 generated after the washing process is passed through the evaporated raw material pipe 22 and the valve 52 to be discharged to the outside by the vacuum exhaust treatment means 54.

However, this residue is accumulated not only in the evaporator 8 but also in the processing chamber 26 (in particular, the inner wall of the processing chamber 26 and the surfaces of the gas diffusion plate 32 and the holder 36). Departure of the residue results in the generation of particles (dust) that adhere to the surface of the substrate 34. In this case, problems such as contamination of the surface of the substrate are generated.

Therefore, a cleaning liquid for dissolving the residue has sometimes been used to clean the interior of the treatment chamber 26. The washing process inside the processing chamber 26 and the washing process inside the evaporator 8 are performed independently. Furthermore, fixed residues are not easily removed by the wash liquor and therefore require a long time to remove the fixed residues. Thus, the time for which the CVD apparatus is stopped is excessively extended, which lowers the throughput (processing capacity per unit time) of the CVD apparatus.

It is an object of the present invention to shorten the time for which the CVD apparatus is stopped by shortening the time required to clean the evaporator.

1 shows a first embodiment of a CVD apparatus in which a cleaning method according to the invention is carried out.

2 is a view showing an example of a washing liquid supply means for supplying the washing liquid in the evaporated state.

3 shows a second embodiment of a CVD apparatus in which a cleaning method according to the invention is carried out.

4 shows an example of a conventional CVD apparatus.

Figure 5 shows a third embodiment of a CVD apparatus having an evaporation apparatus according to the present invention.

FIG. 6 shows an example of a part of the evaporator shown in FIG. 5. FIG.

7 is a view showing an example of a washing liquid supply device for supplying the washing liquid in the evaporated state.

8 shows another example of an evaporation apparatus.

9 is a view partially showing another example of an evaporation apparatus.

10 is a view partially showing another example of an evaporation apparatus.

11 is a view partially showing another example of an evaporation apparatus.

12 shows yet another example of a CVD apparatus having an evaporation apparatus according to the present invention.

13 shows another example showing the structure of an evaporator section;

A first feature of the invention is a method of cleaning a CVD apparatus comprising an evaporator for evaporating a liquid raw material by applying heat and a processing chamber for forming a thin film on a substrate by the CVD method using raw materials evaporated by the evaporator. Injecting a wash solution for dissolving the residues generated in the evaporator and the processing chamber into the evaporator, and then heating the wash solution to evaporate the wash solution while the residue is removed in the evaporator; And removing residues in the process chamber by injecting an exhaust gas containing the gas into the process chamber from the evaporator.

A second aspect of the present invention is a method for cleaning a CVD apparatus having an evaporator for evaporating a liquid raw material by applying heat and a processing chamber for forming a thin film on a substrate by the CVD method using raw materials evaporated by the evaporator. Injecting a wash liquid for dissolving the residues generated in the evaporator and the processing chamber into the evaporator in such a way that the wash liquid is evaporated so that the residue is removed in the evaporator, and the components of the wash liquid And removing residues in the process chamber by injecting an exhaust gas containing the gas into the process chamber from the evaporator.

A third feature of the invention is that in the method of cleaning a CVD apparatus according to the second feature, the evaporator is heated when the residue is removed.

A fourth aspect of the invention is a method of cleaning a CVD apparatus according to any one of the first to third aspects, wherein the exhaust gases injected into the process chamber are used to generate a plasma when residues are removed. It is.

A fifth aspect of the invention is a method for cleaning a CVD apparatus according to the fourth aspect, wherein the inert gas is formed of at least one of nitrogen gas or rare gas when the residue is removed so that the pressure of the gas in the processing chamber is controlled. It is injected into the process chamber.

A sixth aspect of the present invention is an evaporation vessel made of a conductive material to which a liquid raw material is applied, a heater for heating the evaporation vessel to evaporate the liquid applied in the evaporation vessel, and a solution for dissolving residue generated in the evaporation vessel. A position between the electrode means and the evaporation vessel to generate a plasma in the evaporation vessel by using a washing liquid supply means, an electrode means disposed in the evaporation vessel in an electrically insulated manner from the evaporation vessel, and the evaporated washing liquid Provided is a liquid raw material evaporation apparatus having a plasma generating power source for supplying a high frequency electrode or a pulse voltage to the same.

A seventh aspect of the present invention provides an apparatus having the same structure as the apparatus according to the sixth aspect and having gas supply means instead of washing liquid supply means. This gas supply means is for supplying an inert gas composed of at least one of nitrogen gas or rare gas into the evaporation vessel.

An eighth aspect of the invention provides an apparatus having the same structure as the apparatus according to the sixth aspect and having a gas supply means according to the seventh aspect.

A ninth aspect of the present invention is the sixth to eighth aspects, wherein the washing liquid supply means is located inside the evaporation vessel, and the washing liquid is in an evaporated state.

A tenth aspect of the present invention is the sixth to ninth aspect, further comprising a direct current power source for applying a negative direct current bias voltage to the evaporation vessel or the electrode means.

An eleventh aspect of the present invention is that the apparatus for evaporating the liquid raw material according to the sixth to tenth aspects includes magnetic field forming means for forming a magnetic field perpendicular to the electric field generated by the plasma generating electrode.

A twelfth aspect of the present invention includes an apparatus for evaporating liquid raw materials according to the sixth to eleventh aspects, and a processing chamber for forming a thin film on a substrate by a CVD method using raw materials evaporated in the evaporation apparatus. A method of cleaning a CVD apparatus, the method comprising: injecting exhaust gas generated after removing residues in the evaporation vessel by using plasma while the interior of the process chamber is evacuated; and removing residues in the evaporation vessel; And simultaneously generating a plasma in the process chamber by the exhaust gas to remove residues in the process chamber.

A thirteenth aspect of the present invention is a method of cleaning a CVD according to the twelfth aspect, wherein when plasma is generated in the treatment chamber by use of exhaust gas, the evaporated washing liquid for dissolving the residue generated in the treatment chamber is A method of injecting one or more or inert gases into the process chamber is provided.

The above and other objects and features and advantages of the present invention will become more apparent from the following detailed description and claims in conjunction with the accompanying drawings.

(Example)

Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings.

1 shows an example of a CVD apparatus in which a cleaning method according to the present invention is performed. In the components shown in Fig. 4, the same components as those in the conventional example are given the same numbers. Here, description will mainly be made of parts different from the conventional example.

In the present embodiment, the evaporator 8, more specifically, the evaporation vessel 10, is a washing liquid supply means 60 for supplying a washing liquid 64 for dissolving residues generated in the evaporation vessel 10 and the processing chamber 26. It includes.

The washing liquid supply means 60 according to the present embodiment includes a washing liquid container 62 for accommodating the washing liquid 64, valves 66 to 68, and a pipe for connecting the components to each other. The washing liquid container 62 is supplied with the inert gas 50 described above to send the washing liquid 64 using pressure. The washing liquid 64 supplied from the washing liquid supply means 6 is supplied into the evaporation vessel 10 by the liquid raw material pipe 6 and the nozzle 14. The washing liquid 64 is made of, for example, HNO ₃ (nitric acid), HNO ₂ (nitrous acid), H ₂ O ₂ (hydrogen peroxide), HCl (hydrogen chloride), HF (hydrogen fluoride), and the like.

In forming the membrane, valves 68, 44, 45, 47 and 24 are opened and valves 66 so that an inert gas 50 is used to direct the liquid raw material 4 from the liquid raw material supply means 2 using pressure. , 67, 46 and 52). While the flow rate adjusting means 48 adjusts the flow rate of the liquid raw material 4, the liquid raw material 4 is supplied into the evaporation vessel 10 through the nozzle 14. A desired thin film is then formed on the substrate 34 by performing a process such as that performed by the conventional example shown in FIG.

If residues accumulate in the evaporator 10 and / or process chamber of the evaporator 8 and a wash liquid is required, the valves 47 and 24 are preferably closed and the valve 52 is opened. In this way, the inside of the evaporation vessel 10 is exhausted by operating the vacuum exhaust treatment means 54. The valves 52, 44, 45 and 68 are then open and the valves 24, 47, 46, 66 and 67 are closed. Then, the washing liquid is sent from the washing liquid supply means 60 by the inert gas 50 using the pressure. The washing liquid 64 is supplied into the evaporation vessel 10 through the liquid raw material pipe 6 and the nozzle 14 while the flow adjusting means 48 adjusts the flow rate of the washing liquid 64.

At the same time, the evaporation vessel 10 is heated to a level not lower than the evaporation temperature for the washing liquid 64 by the heater 12. As a result, the washing liquid 64 in the evaporation vessel 10 is evaporated to remove residues fixed to the inner walls of the evaporation vessel 10 and the nozzle 14.

The exhaust gas 21 generated after the washing process is performed and supplied from the evaporator 8 passes through the evaporated raw material pipe and the valve 24 and is supplied to the processing chamber 26. In particular, the exhaust gas 21 is supplied to the processing chamber 26 by the vacuum exhaust processing means 40. The exhaust gas 21 contains a large amount of the washing liquid component remaining as a residue in the process of washing the interior of the evaporator 8. The exhaust gas 21 supplied to the processing chamber 26 is diffused into the processing chamber 26 by passing through the gas diffusion plate 32. This exhaust gas 21 then removes residues present in the process chamber 26 (in particular, the inner walls of the process chamber 26, the gas diffusion plate 32 and the holder 36).

After the cleaning process is performed, the exhaust gas 21 passes through the valve 38. In particular, the trapping means 56 traps and adsorbs the components of the cleaning liquid and the components of the residue so that the components are harmless. The exhaust gas 21 is then discharged to the outside by the vacuum exhaust treatment means 40. The trapping means 56 may be provided arbitrarily because it is not an essential component of the present invention.

The washing method according to the present invention is to remove the residue in the evaporator 8 using the washing liquid 64 and to remove the residue in the treatment chamber 26 using the exhaust gas 21 containing the components of the washing liquid. It is possible. Therefore, the total time required to clean the evaporator 8 and the processing chamber 26 can be shortened. Thus, the time for stopping the operation of the CVD apparatus can be shortened. As a result, the throughput of the CVD apparatus can be improved.

Since the same washing liquid 64 can be used to clean the evaporator 8 and the treatment chamber 26, the washing liquid can be saved and the economic effect can be improved compared to the method in which the evaporator 8 and the treatment chamber 26 are independently washed ( Ie twice).

The washing liquid 64 may be supplied to the evaporator 8 in an evaporated state. In this case, for example, a washing solution supply means 60a having a structure as shown in FIG. 2 may be used instead of the washing solution supply means 60.

The washing liquid supply means 60a is a so-called bubbler or bubbling device in which bubbles are generated in the washing liquid 64 by injecting the inert gas 50 into the washing liquid 64 through the valve 66. In this way, the evaporation of the washing liquid 64 is increased, so that the washing liquid 64 is supplied in the evaporation state. When the evaporation process is performed valves 66, 67, 46 and 47 are opened and valves 68, 44 and 45 are closed. In this way, the washing liquid 64 in the evaporated state is supplied to the evaporation vessel 10 through the liquid raw material pipe 6.

When the washing liquid 64 in the evaporated state is supplied to the evaporator 8, the heating of the evaporator 8 by the heater 12 required when the washing process is performed may be omitted. When heating by the heater 12 is used at the same time, the residue dissolving effect of the washing liquid 64 can be improved, so that the residue removing effect in the evaporator 8 is further improved.

When the cleaning process is performed, the exhaust gas 21 supplied to the processing chamber 26 may be used to generate plasma in the processing chamber 26. An example having a structure in this case is shown in FIG.

The example shown in FIG. 3 has a structure in which the portion between the holder 36 and the support column 71 for the holder 36 is electrically insulated by the insulating member 70. In addition, the high frequency power source 72 serving as a plasma generating power source is connected between the holder 36 and the parallel circuit 74 through the parallel circuit 74. The processing chamber 26 and the gas diffusion plate 32 electrically connected to the processing chamber 26 are grounded. As a result of having the above structure, high frequency discharge occurs between the holder 36 and the processing chamber 26 and the gas diffusion plate 32. Therefore, the plasma 76 containing the components of the cleaning liquid is generated in the processing chamber 26.

Since the plasma 76 is generated, the components of the washing liquid are dissolved or electrically dissolved to generate active substances in the components. Due to the etching effect and the sputtering effect of the active material caused by the active material, residues fixed in the interior of the process chamber 26, in particular, the inner wall of the process chamber 26, the gas diffusion plate 32 and the holder 36 are further increased. Can be effectively removed.

There is a method different from that shown in FIG. 3 as a method of supplying high frequency power from the high frequency power source 72. For example, the structure in which the gas diffusion plate 32 is electrically insulated from the process chamber 26 can be used. In this case, since the high frequency power source 72 is connected to the gas diffusion plate 32 through the parallel circuit 74, power can be supplied from the high frequency power source 72. In this case, the processing chamber 26 and the holder 36 are grounded. In this case, the plasma 72 is issued by the high frequency discharge generated between the gas diffusion plate 32, the processing chamber 26, and the holder 36. As a result, residues in the process chamber 26 can be removed.

DC bias power supply for supplying a negative DC bias voltage to the components in the process chamber 26, the gas diffusion plate 32, and the holder 36 can be provided. In this way, positive ions in the plasma 76 are attracted by the negative bias voltage. Thus, most of the residue in the components to which the negative bias voltage is supplied can be removed. In the example shown in FIG. 3, the DC bias power source 78 is inserted in series with the ground line of the processing chamber 26 in such a way that the processing chamber 26 becomes a cathode. Thus, the wall surface of the processing chamber 26 is biased with a negative potential. Therefore, most of the residue on the wall surface is removed by the positive ions in the plasma 76 attract the wall surface of the processing chamber 26.

In order to control the gas pressure of the processing chamber 26, a structure in which a gas injection pipe 80 is connected to the gas injection pipe 28 is used to inject an inert gas 82 made of nitrogen gas or rare gas into the processing chamber. Can be. Gas suitable for inert gas 82 when gas pressure suitable for generating plasma in process chamber 26 (eg, about 10 ⁻¹ Torr to about 10 Torr) cannot be easily achieved only by exhaust gas 21. Pressure can be easily achieved. The inert gas 82 is also formed of plasma in the processing chamber 26. Due to the sputtering effect of the ions in the inert gas plasma and the synergistic effect of the etching of the active substance in the components of the cleaning liquid in the exhaust gas 21 and the sputtering effect, the residue in the processing chamber 26 is effectively removed in a shorter time. As the inert gas 82, a rare gas such as argon gas or xenon gas is preferably used.

5 shows an example of a CVD apparatus having an evaporation apparatus according to the present invention. 6 is a view showing an example of a portion of the evaporator shown in FIG.

In this embodiment, an evaporator 108a is provided.

The evaporator 108a is provided with an evaporation vessel 110 through which the liquid raw material 104 is supplied from the liquid raw material supply device 102 described above through a nozzle 114 and a liquid raw material pipe 106 made of a conductive material, in particular a metal. Equipped. Also, the evaporator 108a includes a heater 112 that heats the evaporation vessel 110 to evaporate the liquid raw material 104 supplied to the evaporation vessel 110 and the washing liquid 154 described later. It is. The heater 112 is an electric heater, for example. The evaporated raw material pipe 122 for supplying the evaporated raw material 120 to the processing chamber 126 is connected to the evaporation vessel 110.

In addition, the evaporator 108a is provided with a washing liquid supply device 150 for supplying the washing liquid 154 into the inside of the evaporating vessel 110 capable of dissolving residues generated in the evaporating vessel 110. In addition, the evaporator 108a is a gas for supplying the inert gas 118 composed of at least one of nitrogen gas or rare gas (that is, He, Ne, Ar, Kr, Xe or Re) to the inside of the evaporation container 110. The supply means 119 is provided.

In this embodiment, the gas supply means 119 is provided with a flow control means 117 for allowing the above-described gas injection pipe 116 and the inert gas 118 to be injected around the nozzle 114.

The washing liquid supply device 150 includes a washing liquid container 152 for accommodating the washing liquid 154, valves 156 to 158, and a pipe for connecting the components. Inert gas 160, which is used to move wash liquor 154 using pressure, is supplied to wash liquor container 152. Inert gas 160 is composed of at least nitrogen gas or rare gas. The cleaning liquid 154 is supplied from the cleaning liquid supply device 150 to the inside of the evaporation container 110 through the liquid raw material supply device 102, the liquid raw material pipe 106, and the nozzle 114 (also serving as a passage). . The washing liquid 154 is made of, for example, HNO ₃ (nitric acid), HNO ₂ (nitrous acid), H ₂ O ₂ (hydrogen peroxide), HCl (hydrogen chloride), HF (hydrogen fluoride), and the like.

In this embodiment, the liquid raw material supply device 102 connects the liquid raw material supply device 102, the valves 144 to 147, the flow control means 148, and the components to receive the liquid raw material 104. It is equipped with a pipe for giving. The line positioned between the valve 144 and the valve 146 is supplied with an inert gas 160 supplied from the washing liquid supply device 50.

The nozzle 114 is inserted into the evaporation vessel 110 through the hollow insulating member 170. The insulating member 17 electrically insulates the section between the evaporation vessel 110 and the nozzle 114. The nozzle 114 is made of a conductive material, in particular metal. In this embodiment the nozzle 114 forms the electrode means.

The liquid raw material pipe 106 is electrically insulated from the vicinity of the evaporation vessel 110 by the hollow insulating member 168. The plasma generating power source 172A is connected to a position between the liquid raw material pipe 106a and the ground portion connected to the nozzle 114 through the parallel circuit 174. In this embodiment, the plasma generating power source 172a is a high frequency power source that generates a high frequency power of 13.56 MHz output. The evaporation vessel 110 according to the present embodiment is electrically connected to the processing chamber 126 through the evaporation raw material pipe 122 and the valve 124 described above. The processing chamber 126 is grounded. Therefore, high frequency power can be supplied from the plasma generating power source 172a to the section between the nozzle serving as the electrode means and the evaporation vessel 110.

In general, sealing packing is provided between the insulating member 170 and the evaporation vessel 110 positioned to be in contact with the insulating member 170, and between the insulating member 170 and the liquid raw material pipe 160a, respectively. Located. Encapsulation packing is not shown in the figures. In addition, the sealing packing for the insulating member 168 and the insulating members 178 and 180 is also not shown.

Referring to FIG. 5, trapping means 164 for trapping and adsorbing a predetermined component in the exhaust gas treatment means 66 for exhausting the inside of the evaporation vessel 110 and the exhaust gas 121 supplied from the evaporation vessel 110. Is connected to the evaporated raw material pipe 122 through valve 162. The trapping means 164 is not an essential component of the present invention and may be provided arbitrarily. The above description may also be applied to the embodiment shown in FIG. 12.

The processing chamber 126 has a holder 136 for supporting the substrate 134, which is a thin film, and a plurality of small openings, and a gas diffusion plate 132 disposed to diffuse the injected gas into the processing chamber 126. It is provided. The holder 136 and the substrate 134 positioned on the holder 136 are heated by heating means (not shown). Vacuum exhaust processing means 140 for evacuating the interior of the processing chamber 126 is supplied to the processing chamber 126 through the valve 138. When a film made of SrTiO ₃ is formed, the base 130 is a mixed gas of TTIP and an oxide gas (O _2, etc.).

The operation of the CVD apparatus having the evaporator 108a shown in FIG. 5 will now be described. Once the membrane is formed, valves 158, 144, 145, 147 and 124 open and valves 156, 157, 146 and 162 close. In this way, the liquid raw material 104 is supplied from the liquid raw material supply device 102 by the inert gas 160 using pressure. While the flow rate adjusting means 148 adjusts the flow rate of the inert gas 160, the liquid raw material 104 is supplied into the evaporation vessel 110 through the nozzle 114.

At the same time inert gas 118 is supplied to the gas injection pipe 116. In addition, the evaporation vessel 110 is heated to a temperature higher than the evaporation temperature for the liquid raw material 104 by the heater 112. When the liquid raw material 104 contains Sr (DPM) ₂ or Ba (DPM) ₂ , the evaporation vessel 110 is heated to a temperature not lower than about 250 ° C.

In this way, the liquid raw material 104 is roughly granulated and ejected from the nozzle 114, and then dispersed and collided with a wide portion of the inner wall of the evaporation vessel 110, thereby instantaneously evaporating the liquid raw material 104. The evaporated raw material 120 passes through the evaporative raw material pipe 122 and the valve 124 and then is supplied to the process chamber 126 by the pressure difference. The raw material 120 and the gas 130 are mixed with each other in the processing chamber 126 and the mixed gas is dispersed by the gas diffusion plate 132 to have a constant flow rate. This mixed gas is then dispersed in the processing chamber 126 evacuated by the vacuum evacuation means 140. This mixed gas then comes into contact with the surface of the heated substrate 134 and a CVD reaction occurs to form a thin film of material such as SrTiO ₃ on the substrate 134. Part of the mixed gas is discharged to the outside through the vacuum exhaust treatment means 140.

If residues accumulate in the evaporation vessel 110 of the evaporator 8a and cleaning is to be performed, the valves 124, 144, 145 and 158 are closed and the valves 162, 147, 146, 156 and 157 are opened. do. In this way, the washing liquid 154 is discharged from the washing liquid supply device 150 by the inert gas 160 using the pressure. The washing liquid 154 is supplied into the evaporation vessel 110 through the liquid raw material pipe 106 and the nozzle 114 while the flow rate adjusting means 148 adjusts the flow rate. At the same time, the evaporation vessel 100 is heated to a temperature not lower than the evaporation temperature for the washing liquid 154 by the heater 112. As a result, the evaporated washing liquid 154 having a predetermined pressure is present in the evaporation vessel 110.

In the above description, the high frequency power is supplied from the plasma generating power source 172a to the position between the nozzle 114 and the evaporation vessel 110. Therefore, since the high frequency discharge occurs between the nozzle 114 and the inner wall of the evaporation vessel 110, the plasma 176, which is the cleaning liquid 154 whose components are evaporated, is generated.

As a result of the generation of the plasma 176, the components of the cleaning liquid 154 are dissolved or electrically dissolved, thereby generating an active material in the cleaning liquid 154. Due to the etching effect and the sputtering effect of the active material, residues fixed in the inner wall of the evaporation vessel 110, in particular, the inner wall of the evaporation vessel 110 and the nozzle 114 can be effectively removed in a short time. As a result, the evaporator 108a can be operated stably for a long time.

After the washing process is performed, the exhaust gas 121 as described above existing in the evaporation vessel 110 passes through the evaporated raw material pipe 122 and the valve 162. In this embodiment the components of the wash liquor and their residues are adsorbed and removed by the trapping means 164, thus not causing any harm. This component is then discharged to the outside by the exhaust treatment means 166.

When the inside of the evaporation vessel 110 is washed, the inert gas 118 described above may be supplied from the gas supply means 119 to the evaporation vessel 110. If a high gas pressure (for example about 10 ⁻¹ Torr to about 10 Torr) sufficient to generate a plasma in the evaporation vessel 110 cannot be easily achieved only by evaporation of the cleaning liquid 54, an inert gas ( 118) can easily achieve a sufficiently high gas pressure. Inert gas 118 is also formed in the plasma in the evaporation vessel (110). Due to the sputtering effect caused by the ions in the inert gas plasma and the synergistic effect of the etching and sputtering effects caused by the active substances in the components of the cleaning liquid, the residues fixed in the evaporation vessel 110 are more effectively Can be removed. In this case, since the sputtering ratio can be increased from the inert gas 118, it is preferable to use rare gases such as Ar and Xe.

A method of generating the plasma 176 by the inert gas 118 may be used by supplying only the inert gas 18 from the gas supply means 119 without supplying the washing liquid 154 into the evaporation vessel 110. In this case, due to the sputtering effect of ions in the inert gas plasma, residues fixed in the evaporation vessel 110 may be effectively removed within a short time.

Alternatively, for example, as shown in FIG. 8, the washing solution supply device 150a may be used instead of the evaporated washing solution 154. The cleaning liquid supply device 150a is a so-called bubbler or bubbling device in which bubbles are generated in the cleaning liquid 154 by injecting the inert gas 160 into the cleaning liquid 154 through the valve 156. In this way, the evaporation of the washing liquid 154 increases, so that the washing liquid 154 is supplied in an evaporated state. When the evaporation process is performed, valves 156, 157, 146 and 147 are opened and valves 158, 144 and 145 are closed. Thus, the washing liquid 154 in the evaporated state is supplied to the evaporation vessel 110 through the liquid raw material pipe 106.

Since the washing liquid 154 in the evaporated state can be supplied to the evaporating vessel 110 by using the washing liquid supplying device 150a as described above, the evaporating vessel 110 is provided to the heater 112 when the washing process is performed. Heating is not necessary. In particular, the gas pressure in the evaporation vessel 110 can easily control the plasma generation to a satisfactory level, such as when the liquid wash liquid 154 has a structure in which the liquid washing liquid 154 evaporates by heating in the evaporation vessel 110. At the same time, the heat generated by the heater 112 may be used.

5 and 6, the evaporation raw material pipe 122, the processing chamber 126, and the gas injection pipe 116 are electrically connected to the evaporation vessel 110. Therefore, the potentials of the components are all the same. Thus, large loops are electrically formed in all parts of the device. Therefore, the high frequency power is supplied from the plasma generating power source 172a to the position between the nozzle 14 and the ground portion, thereby generating the plasma in an unexpected section. In this case, the efficiency of supplying high frequency power to the plasma 176a generated in the evaporator 108 is lowered. In order to prevent this, for example, as shown in FIG. 8, hollow insulation at an intermediate position (preferably adjacent to the evaporation vessel 110) between the evaporation raw material pipe 122 and the gas injection pipe 116 is shown. It is preferable to have the member 178. In this way electrical insulation is achieved between all the supporting members and pipes connected to the evaporation vessel 110 and the evaporation vessel 110. In addition, the evaporation vessel 110 is firmly grounded.

Instead of the plasma generating power source 172a and the parallel circuit 174, which are high frequency power sources, for example, as shown in FIG. 9, at a position between the nozzle 114 and the evaporation vessel 110, which serve as an electrode means. The plasma generating power supply 172b for supplying the switching for generating the output DC voltage by turning on / off (switching) the DC power supply 182 for generating the output DC voltage, and the DC voltage supplied from this DC power supply 182. Means 184 are provided. The output voltage generated from the DC power supply 182 is, for example, about 500 V to about 10 KV. The switching means 184 are operated in such a way that when the switching means 184 is on, the pulse width is for example from about 1 s to about 1 kHz and the duty ratio is from about 0.1% to about 10%. The gas pressure in the evaporation vessel is necessary to determine according to Paschen's Law.

In the structure shown in FIG. 9, the plasma 176 may be generated in the evaporation vessel 110 by the high-pressure pulse discharge generated between the nozzle 114 and the evaporation vessel 110. In this case, the polarity of the supplied pulse voltage, that is, the polarity of the DC power supply 182 is such that the evaporation vessel 110 or the nozzle 114 that needs to be cleaned becomes the cathode (in the illustrated structure, the nozzle 114 is In a manner such that it becomes a cathode). Thus, the cations in the plasma 176 attract the cathode side element, thereby improving the sputtering effect. Thus, negative electrode element residues can be removed.

Although a method of generating a direct current arc discharge in the evaporation vessel 110 may be used to generate the plasma 176, the nozzle 14 and the evaporation vessel 110 may be excessively damaged by the direct current arc discharge. Therefore, it is preferable to use the pulse discharge described above.

For the same reason, when the plasma generating power source 172a, which is a high frequency power source, is used as the nozzle 114 or the evaporation container 110, the DC bias power source 186 for supplying the negative DC bias voltage as in the embodiment shown in FIG. ) Can be provided. In this case, positive ions in the plasma 176 are attracted by the negative bias voltage. Therefore, most of the residue of the component to which the negative bias voltage is supplied can be removed. The DC bias power source 186 may be inserted in series between the evaporation vessel 110 and the ground portion as in the embodiment shown in FIG. 10 or may be inserted in series with the line of the plasma generating power source 172a. As can be seen from the above description, the direction of the DC bias power supply 186 may be opposite to that shown in the figure.

As shown in FIG. 11, magnetic field forming means for forming a magnetic field B perpendicular to the electric field E generated by the plasma generating power source 172b or 172a may be provided in the evaporation vessel 110. In the embodiment shown in Figure 11 the magnetic field forming means is a cylindrical magnetic coil 188 located outside of the evaporation vessel (110). As a result, the magnetic field B is formed in the axial direction of the evaporation vessel 110, which is a direction perpendicular to the electric field E formed in the basic direction of the evaporation vessel 110. Permanent magnets may be used instead of the magnetic coil 188. The plasma generating power source may be a plasma generating power source 172b for generating a pulse voltage output having a form as shown in the drawing, or may be the aforementioned plasma generating power source 172a for generating a high frequency power output. In the latter case, despite the difference that the electric field (E) changes over time, the electric field (E) and the magnetic field (B) are perpendicular to each other.

As described above, when the electric field E and the magnetic field B are perpendicular to each other in the evaporation vessel 110, plasma may be effectively localized in the evaporation vessel 110 due to a so-called coaxial magnetron discharge. Therefore, the speed at which residues in the evaporation vessel 110 are removed can be further increased.

The structure of the evaporation vessel may be formed by stacking disks as shown in FIG. 13 as well as the nozzle type described above. The evaporator disclosed in US Pat. No. 5,361,800 has the structure as described above. That is, the raw material supply pipe 206 connected to the liquid raw material pipe 106 is inserted into the evaporation vessel 110. A plurality of openings 208 are formed in the wall surface adjacent to the tip of the raw material supply pipe 206. In addition, a plurality of metal disks 210 are stacked around the opening 208 to form a gap. Therefore, the liquid raw material 4 is ejected through the gap and discharged to the periphery thereof. The heater 112 is inserted into the evaporation vessel 110 such that each of the disks 210 is heated through the evaporation vessel 110, the raw material supply pipe 206, and the like. The liquid raw material 4 ejected from the position adjacent to the central portion of the disk 210 is heated at the periphery of the heating disk 210 and evaporated. The evaporated raw material 120 passes through the evaporated raw material pipe 122 connected to the other end of the evaporation vessel 110 and then is discharged.

Since the above-described embodiment has a structure in which the raw material supply pipe 206 and the plurality of disks 210 connected to the raw material supply pipe 206 serve as electrode means, the above-described components are electrically connected from the evaporation vessel 110. Is insulated by the insulating member 212 and is electrically connected to the evaporation vessel 110. The high frequency power or the pulse voltage is supplied to the position between the raw material supply pipe 206 and the disk 210 and the evaporation vessel 110 by the plasma generating power source 172a or 172b to evaporate the vessel by the liquid raw material evaporated therein. Plasma is generated in 110. As a result, the residue in the evaporation vessel 110 can be effectively removed.

When an inert gas 118 is also used to clean the interior of the evaporation vessel 110, the structure of the embodiment shown in Figure 13 is a gas injection pipe 116 forming a gas supply means 119 is evaporation vessel 110 ), The inert gas 18 is supplied to the evaporation vessel 110.

A structure and method for removing the residue in the process chamber 126 while removing the residue in the evaporation vessel 110 is shown in FIG.

In this case, valve 162 is closed and valves 124 and 138 are open. Therefore, while the inside of the processing chamber 126 is evacuated by the vacuum exhaust treatment means 140, the exhaust gas 121 supplied from the evaporation vessel 110 and generated after the washing process is carried out to the processing chamber 126. Supplied. The exhaust gas 121 is also used to generate the plasma 204 in the process chamber 126. The plasma 204 simultaneously removes residues in the process chamber 126, particularly those fixed on the inner walls of the process chamber 126, the gas diffusion plate 132, and the holder 136, simultaneously with the internal cleaning process of the evaporation vessel 110. Used to remove

That is, the exhaust gas 121 supplied from the evaporation vessel 110 and generated after the washing process is performed is a component of the gas used to clean the inside of the evaporation vessel, in particular at least the evaporated washing liquid 154 or the inert gas 118. It contains a component consisting of one of). Therefore, when the plasma 204 having the above-described gas component is generated in the processing chamber 126, the residue in the processing chamber 126 can be effectively removed in a short time due to the etching effect and / or sputtering effect caused from the plasma. When residue removal in the evaporation vessel 10 and residue removal in the treatment chamber 126 are performed as described above, the time required for cleaning the CVD apparatus can be significantly shortened.

In the structure shown in FIG. 12, the plasma 204 is generated in the processing chamber 126 by electrically insulating the section between the holder 136 and the support column 192 by the insulating member 190. In addition, the high frequency power source 194 serving as a power source for generating plasma is connected to a position between the holder 136 and the ground portion through the parallel circuit 196. The processing chamber 126 and the gas diffusion plate 132 electrically connected to the processing chamber 126 are grounded. As a result of the above-described structure, a high frequency discharge occurs between the holder 136, the processing chamber 126, and the gas diffusion plate 132, thereby generating the plasma 204.

In this embodiment a trapping means 164 is provided between the valve 138 and the vacuum exhaust treatment means 140 for trapping and adsorbing the residue and washing liquid components. The exhaust gas after the inside of the processing chamber 126 has been cleaned becomes harmless in the trapping means 164 and is then discharged to the outside by the vacuum exhaust treatment means 140.

The method of supplying the high frequency power from the high frequency power source 194 is different from the method shown in FIG. 12. For example, a structure in which the gas diffusion plate 132 is electrically insulated from the process chamber 126 may be used. In addition, since the high frequency power source 194 is connected to the gas diffusion plate 132 through the series circuit 196, power is supplied from the high frequency power source 194. In this case, the processing chamber 126 is grounded. The holder 136 is also preferably grounded, but may be up away from the ground portion. Also in this case, the plasma 204 is generated in the processing chamber 126 by the high frequency discharge occurring between the gas diffusion plate 132 and the processing chamber 126 as in the above-described structure. As a result, residues in the process chamber 126 can be removed.

Similar to the embodiment shown in FIG. 10, a direct current bias power supply may also be provided for supplying a negative direct current bias voltage to the component to be cleaned. In this case, most of the residue in the component to which the negative bias voltage is applied can be removed.

As in the embodiment illustrated in FIG. 9, the plasma 204 may be generated by using a plasma generating power source for generating an output pulse voltage instead of the high frequency power source 194 and the series circuit 196.

As described above, the inside of the evaporation vessel 110 and the inside of the processing chamber 126 are simultaneously washed, and the gas pressure in the evaporation vessel 110 is discharged in the evaporation vessel 110 (to generate plasma. When maintained at a suitable level, the gas pressure in the process chamber 126 is naturally lower than the gas pressure in the evaporation vessel 110. This is because the processing chamber 126 is located adjacent to the vacuum exhaust processing means 140, and the conductance of the gas is lowered by the evaporated raw material pipe 122 or the like. Therefore, since the gas pressure in the processing chamber 126 becomes very low, discharge occurs in the processing chamber 126 (plasma is generated). In this case, at least one of the above-mentioned evaporated washing liquid or the above-mentioned inert gas (ie, nitrogen gas or rare gas) may be additionally injected into the processing chamber 126 by the exhaust gas 121. As a result, the gas pressure in the processing chamber 126 as well as the gas pressure in the evaporation vessel 110 can be maintained at a level suitable for generating plasma. In order to achieve this, the valve 158 and the gas injection pipe 128 of the cleaning liquid supply device 50a, for example, the pipe 198, the valves 200 and 201 and the flow rate adjusting means (as shown in FIG. 202 is connected to each other. As a result, at least one of the washing liquid 154 or the inert gas 160 that is evaporated in the washing liquid supply device 150a may be supplied into the processing chamber 126.

When the discharge can be maintained in the evaporation vessel 110 even though the gas pressure is relatively high, the valve 138 may be a valve for adjusting the opening degree, so that the process chamber 126 is at a level suitable for discharge. The pressure of the gas inside can be maintained.

Since the present invention has the structure as described above, the following effects can be obtained.

According to the first aspect of the present invention, the residue removal in the evaporator by the use of the washing liquid and the residue removal in the treatment chamber by the use of the exhaust gas containing the components of the washing liquid can be simultaneously performed. Thus, the total time required to clean the evaporator and the treatment chamber can be shortened. Therefore, the time for stopping the operation of the CVD apparatus can be shortened. As a result, the throughput of the CVD apparatus can be increased. In addition, the same washing solution may be used for the washing process of the evaporator and the treatment chamber. Therefore, the cleaning liquid can be saved and the economic effect can be increased.

According to a second aspect of the present invention, it has a structure in which the washing liquid in the evaporated state is injected into the evaporator. Therefore, the heating process in the evaporator required when the washing process is performed can be omitted.

According to a third aspect of the invention, the washing liquid in the evaporation state is introduced into the evaporator and in such a way that heating of the evaporator is performed. Therefore, the residue dissolving effect of the washing liquid can be improved. As a result, the effect of removing residues in the evaporator is also improved.

According to a fourth aspect of the present invention, a plasma is generated by using an exhaust gas that generates an active substance among components of the cleaning liquid in the processing chamber. Therefore, the residue fixed in the process chamber can be more effectively removed due to the etching effect and the sputtering effect of the active material.

According to the fifth aspect of the present invention, a gas pressure suitable for generating plasma in a processing chamber can be easily realized. Since the inert gas is formed into the plasma in the processing chamber, since the inert gas is formed into the plasma in the processing chamber, the sputtering effect caused by the ions in the inert gas plasma and the etching effect and the sputtering effect of the active material among the components of the cleaning liquid are accompanied. Due to the effect, residues fixed inside the process chamber can be effectively removed in a shorter time.

According to a sixth aspect of the present invention, plasma can be generated in an evaporation vessel by using the evaporated washing liquid. Plasma is generated to produce an active material in the components of the wash solution. Therefore, due to the etching effect and the sputtering effect of the active material, residues that can be fixed inside the evaporation vessel can be effectively removed in a short time.

According to the seventh aspect of the present invention, plasma can be generated by using an inert gas. Therefore, due to the sputtering effect of ions in the plasma, residues fixed in the evaporation vessel can be effectively removed in a short time.

According to the eighth aspect of the present invention, plasma can be generated by using an evaporated washing liquid and an inert gas. Therefore, due to the etching effect and the sputtering effect of the active substance in the washing liquid and the sputtering effect of the ions in the inert gas, the residue fixed in the evaporation vessel can be effectively removed in a short time.

According to a ninth aspect of the present invention, the washing liquid in the evaporated state may be supplied into the evaporation vessel. Therefore, the gas pressure in the evaporation vessel can be adjusted to a level suitable to generate a plasma having the same structure as compared with when the liquid washing liquid is heated in the evaporation vessel and evaporated.

According to a tenth aspect of the present invention, a negative DC bias voltage may be applied to the evaporation vessel or the electrode means. Since the sputtering and etching effects of the component applied with the negative bias voltage can be improved, most of the residue fixed to the component applied with the negative bias voltage can be removed.

According to the eleventh aspect of the present invention, the plasma can be effectively restricted in the evaporation vessel due to the coaxial magnetron discharge. Therefore, the speed at which residues in the evaporation vessel are removed can be made faster.

According to the twelfth aspect of the present invention, the residue fixed in the interior of the evaporation vessel can be removed and at the same time, the plasma can be effectively removed in the process chamber using the plasma. Therefore, the time required for cleaning the CVD apparatus can be significantly shortened.

According to a thirteenth aspect of the present invention, the gas pressure in the processing chamber can be easily maintained at a level suitable for generating plasma. Therefore, residues in the evaporation vessel and the processing chamber can be more effectively removed.

Claims (13)

A method for cleaning a CVD apparatus comprising an evaporator for evaporating a liquid raw material by applying heat and a processing chamber for forming a thin film on a substrate by a CVD method using raw materials evaporated by the evaporator, Injecting a wash solution to dissolve the residues generated in the evaporator and the treatment chamber into the evaporator and then heating the wash solution to evaporate the wash solution while the residue is removed in the evaporator; And removing the residue in the processing chamber by injecting exhaust gas containing the components of the cleaning liquid from the evaporator into the interior of the processing chamber. The method of claim 1, Exhaust gas injected into the processing chamber is used to generate a plasma when the residue is removed. The method of claim 2, And at least one of nitrogen gas or rare gas is injected into the process chamber when the residue is removed so that the pressure of the gas in the process chamber is controlled. A method for cleaning a CVD apparatus comprising an evaporator for evaporating a liquid raw material by applying heat and a processing chamber for forming a thin film on a substrate by a CVD method using raw materials evaporated by the evaporator, Injecting a wash liquid for dissolving the residues generated in the evaporator and the process chamber into the evaporator in such a way that the wash liquid is evaporated so that the residue is removed in the evaporator; And removing the residue in the processing chamber by injecting exhaust gas containing the components of the cleaning liquid from the evaporator into the interior of the processing chamber. The method of claim 4, wherein And the evaporator is heated when the residue is removed. The method of claim 4, wherein Exhaust gas injected into the processing chamber is used to generate a plasma when the residue is removed. The method of claim 6, And at least one of nitrogen gas or rare gas is injected into the process chamber when the residue is removed so that the pressure of the gas in the process chamber is controlled. Evaporation container made of a conductive material in which a liquid raw material is injected, A heater for heating the evaporation vessel to evaporate the liquid applied in the evaporation vessel, Supplying an inert gas composed of at least one of a nitrogen gas and a rare gas, and a washing liquid supply means for supplying a washing liquid for dissolving the residue generated in the evaporating vessel to the inside of the evaporating vessel. At least one of the gas supply means for, Electrode means disposed in the evaporation vessel in a manner that is electrically insulated from the evaporation vessel, and And a plasma generating power supply for supplying a high frequency power or a pulse voltage at a position between the electrode means and the evaporation vessel to generate a plasma in the evaporation vessel by using the evaporated washing liquid and the rare gas. Evaporator. The method of claim 8, The washing liquid supply means is a liquid material evaporator, characterized in that for supplying the washing liquid in the evaporated state into the interior of the evaporation vessel. The method of claim 9, And a direct current power source for applying a negative direct current bias voltage to the evaporation vessel or the electrode means. The method of claim 10, And a magnetic field forming means for forming a magnetic field perpendicular to the electric field generated by the plasma generating power source. A method of washing a CVD apparatus comprising an apparatus for evaporating a liquid raw material according to claim 8 and a processing chamber for forming a thin film on a substrate by a CVD method using the raw material evaporated in the evaporation apparatus. Injecting exhaust gas generated after removing the residue in the evaporation vessel by using plasma while the inside of the processing chamber is vacuum evacuated; And generating a plasma in the processing chamber by using the exhaust gas to remove residues in the evaporation vessel and simultaneously remove residues in the processing chamber. The method of claim 12, When plasma is generated in the processing chamber by use of the exhaust gas, at least one of evaporated washing liquid or inert gas for dissolving the residue generated in the processing chamber is injected into the processing chamber. How to wash.